Method of controlling plant growth

ABSTRACT

HERBICIDAL USE OF COMPOUNDS OF THE FORMULA   (RN-C6H4-SO2-N-CO-N(-R2)-R&#39;&#39;)(-) HN(+)(-R6)(-R7)-R8   WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF CHLORO, CARBON ATOMS, ALKOXY HAVING A MAXIMUM OF FOUR CARBROMO, IODO, CYANO, ALKYL HAVING A MIXIMUM OF FOUR BON ATOMS, NITRO, AMINO AND THE GROUP   -NH-CO-R3   WHEREIN R3 IS HYDROGEN OR ALKYL HAVING A MAXIMUM OF FOUR CARBON ATOMS, N IS THE INTEGER ONE TO THREE, PROVIDED THAT WHEN N IS ONE, R IS SUBSTITUTED IN THE 4&#39;&#39;-POSITION OF THE PHENYL RING, R&#39;&#39; AND R2 ARE EACH INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING A MAXIMUM OF TWELVE CARBON ATOMS, ALKOXY HAVING A MAXIMUM OF FIVE CARBON ATOMS, ALKYNYL HAVING AT LEAST THREE AND A MAXIMUM OF FIVE CARBON ATOMS, CYCLOALKENYL HAVING AT LEAST FIVE AND A MAXIMUM OF SEVEN CARBON ATOMS, CYCLOALKYL HAVING AT LEAST FIVE AND A MAXIMUM OF SEVEN CARBON ATOMS, MONO SUBSTITUTED CYCLOALKYL SAID SUBSTITUENT BEING ALKYL HAVING A MAXIMUM OF FOUR CARBON ATOMS, PHENYL, SUBSTITUTED PHENYL HAVING A MAXIMUM OF THREE SUBSTITUENTS SAID SUBSTITUENTS BEING SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING A MAXIMUM OF FOUR CARBON ATOMS, BROBROMINE AND THE ROUP FOUR CARBON ATOMS, TRIFLUOROMETHYL, PHENOXY, MONO AND DIHALOGENATED PHENOXY SAID HALOGEN BEING CHLORINE OR BROME AND THE GROUP   -OOC-N(-R4)-R5   SAID GROUP BEING IN THE 3-POSITION WHEREIN R4 AND R5 ARE EACH INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL HAVING A MAXIMUM OF FOUR CARBON ATMS, R6 R7 AND R8 ARE EACH INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING A MAXIMUM OF TWELVE CARBON ATOMS, ALKENYL HAVING A MAXIMUM OF SIX CARBON ATOMS PROVIDED THAT THE ACETYLENIC LINKAGE IS NOT ON THE CARBON ATTACHED TO THE NITROGEN, HYDROXYALKYL HAVING A MAXIMUM OF SIX CARBON ATOMS, TWO OF THE GROUPS R5, R6 AND R7 CAN BE JOINED TOGETHER TO FORM AN ALKYLENE HAVING FOUR TO SEVEN CARBON ATOMS, PROVIDED THAT WHEN TWO OF THE GROUPS R5, R6 AND R7 ARE JOINED TOGETHER THE REMAINING GROUP IS HYDROGEN, AND FURTHER PROVIDED THAT THE GROUPS R5, R6 AND R7 ARE NOT ALL HYDROGEN.

United States Patent Oflice Patented May 29, 1973 U.S. C]. 71-103 16 Claims ABSTRACT OF THE DISCLOSURE Herbicidal use of compounds of the formula R 7 (III) RTE e $/Rfl wherein R is selected from the group consisting of chloro, bromo, iodo, cyano, alkyl having a maximum of four carbon atoms, alkoxy having a maximum of four carbon atoms, nitro, amino and the group wherein R is hydrogen or alkyl having a maximum of four carbon atoms; n is the integer one to three, provided that when n is one, R is substituted in the 4-position of the phenyl ring; R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of twelve carbon atoms, alkoxy having a maximum of five carbon atoms, alkynyl having at least three and a maximum of five carbon atoms, cycloalkenyl having at least five and a maximum of seven carbon atoms, cycloalkyl having at least five and a maximum of seven carbon atoms, mono substituted cycloalkyl said substituent being alkyl having a maximum of four carbon atoms, phenyl, substituted phenyl having a maximum of three substituents said substituents being selected from the group consisting of alkyl having a maximum of four carbon atoms, bromine, chlorine, hydroxy, alkoxy having a maximum of four carbon atoms, trifiuoromethyl, phenoxy, mono and dihalogenated phenoxy said halogen being chlorine or bromine and the group --OCN said group being in the 3-position wherein R and R are each independently selected from the group consisting of hydrogen and alkyl having a maximum of four carbon atoms; R, R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of twelve carbon atoms, alkenyl having a maximum of six carbon atoms provided that the acetylenic linkage is not on the carbon attached to the nitrogen, hydroxyalkyl having a maximum of six carbon atoms, two of the groups R R and R can be joined together to form an alkylene having four to seven carbon atoms, provided that when two of the groups R 1\ and R are joined together the remaining group is hydrogen, and further provided that the groups R R and R are not all hydrogen.

This application is a continuation-in-part of Ser. No. 406,884, filed Oct. 27, 1964, which in turn is a division of 210,217, filed July 16, 1962, both now abandoned.

This invention relates to the control of plant growth by the application of a herbicidal efiective amount of an amine salt of substituted benzenesulfonyl urea.

The anionic portion of the salts of substituted benzenesulfonyl urea is a resonance hybrid i -mi which has the terminologoy of isourea or urea depending upon the charge location. For convenience the terminology isourea and the hybrid formula will be used in the specification and claims.-

The effective compounds of this invention are of the formula Rn O R2 G R6 wherein R is selected from the group consisting of chloro, bromo, iodo, cyano, alkyl having a maximum of four carbon atoms, alkoxy having a maximum of four carbon atoms, nitro, amino and the group wherein R is hydrogen or alkyl having a maximum of four carbon atoms; n is the integer one to three, provided that when n is one, R is substituted in the 4'-position of the phenyl ring; R and R each independently selected from the group consisting of hydrogen, alkyl having a maximum of twelve carbon atoms, alkoxy having a maximum of five carbon atoms, alkynyl having at least three and a maximum of five carbon atoms, cycloalkenyl having at least five and a maximum of seven carbon atoms, cycloalkyl having at least five and a maximum of seven carbon atoms, mono substituted cycloalkyl said substituent being alkyl having a maximum of four carbon atoms, phenyl, substituted phenyl having a maximum of three substituents said substitutents being selected from the group consisting of alkyl having a maximum of four carbon atoms, bromine, chlorine, hydroxy, alkoxy having a maximum of four carbon atoms, trifiuoromethyl, phenoxy, mono and dihalogenated phenoxy said halogen being chlorine or bromine and the group 4 OCN said group being in the 3-position wherein R and R are each independently selected from the group consisting of hydrogen and alkyl having a maximum of four carbon atoms; R, R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of twelve carbon atoms, alkenyl having a maximum of six carbon atoms, alkynyl having at least three and a maximum of six carbon atoms provided that the acetylenic linkage is not on the carbon attached to the nitrogen, hydroxyalkyl having a maximum of six carbon atoms, two of the groups R R and R can be joined together to form an alkylene having four to seven carbon atoms, provided that when two of the groups R R and R are joined together the remaining group is hydrogen, and further provided that the groups R R and R are not all hydrogen.

A preferred embodiment of this invention is when the compounds are of the formula HNR7 wherein R is selected from the group consisting of chloro, 'bromo, iodo, nitro, amino and the group HO Ill NOR3 wherein R is hydrogen, alkyl having a maximum of four carbon atoms, R is selected from the group consisting of hydrogen, alkyl having at least seven and a maximum of twelve carbon atoms, alkoxy having a maximum of four carbon atoms, alkynyl having'at least three and a maximum of five carbon atoms, cycloalkenyl having at least five and a maximum of seven carbon atoms, cycloalkyl having at least five and a maximum of seven carbon atoms, mono substituted cycloalkyl said substituent being alkyl having a maximum of four carbon atoms, mono substituted phenyl, said substituents being selected from the group consisting of alkoxy having a maximum of four carbon atoms, hydroxy, trifluoromethyl, phenoxy, mono and dihalogenatedphenoxy said halogens being chlorine or bromine and the group R4 -O'C-N/ said group being in the 3-position, wherein R and R are each independently selected from the group consisting of hydrogen and alkyl having a maximum of four carbon atoms; R is selected from the group consisting of hydrogen and alkyl having a maximum of three carbon atoms; and R R and R are as previously defined.

A more preferred embodiment of this invention is of the formula wherein R is hydrogen, alkyl having a maximum of four,

carbon atoms, R is selected from the group consisting of hydrogen, alkyl having at least seven and a maximum of twelve carbon atoms, alkoxy having a maximum of four carbon atoms, alkynyl having at least three and a maximum of five carbon atoms, cycloalkenyl having at least five and a maximum of seven carbon atoms, cycloalkyl having at least five and a maximum of seven carbon atoms, mono substituted cycloalkyl said substituent being alkyl having a maximum of four carbon atoms, \m'ono substituted phenyl, said substituent being selected "from the group consisting of alkoxy having a maximum of four carbon atoms, hydroxy, trifluoromethyl, phenoxy, mono and dihalogenated phenoxy said halogens being chlorine or bromine and the group said group being in the 3-position, wherein R and R are each independently selected from the group 'consistingof hydrogen and alkyl having a maximum of four carbon atoms; R is selected from the group consisting of hydrogen and alkyl having a maximum of three carbon atoms.

Amines useful for the preparation of the amine salts of substituted benzenesulfonyl ureas include, but is not limited to dimethyl amine, allylamine, diallylamine, ethanolamine, diethanolamine, hexamethyleneimine, butylamine, di-tertiary butylamine, propylamine, dipropylamine, proparglamine, di-proparglamine, propargl-isopropylamine, methylbutylamine, 2 ethylhexylamine, dodecylamine, diisopropylamine, and the like.

Methods for the preparation of benzenesulfonyl ureas are known in the art. The following illustrate the known procedures for preparation of these compounds:

IV-N

'1 he amine salts are then prepared by the reaction of an excess of amine compound with the substituted benzenesulfonyl urea. This procedure is illustrated by the following exa-mplelf the amine is a gas or a high vapor pressure, the reaction can be carried out under pressure. Quantities are expressed in parts by weight unless otherwise designated. 1

EXAMPLE 1 To a suitable vessel is charged 6.5 parts of p-nitro- 'benzenesulfonyl urea and approximately 2.2 parts dimethylamine. The resultant mixture was heated withstirring until the excess dimethylamine was evaporated. The crude solid which remained was recrystallized from ethanol. A 99% yield of the pale yellow solid product, M.P. 137.6- 138.4. was obtained.

Other examples of compounds prepared are:

dimethylamino salt of p-nitrobenzenesulfonylisourea n-dodecylamino salt of p-nitrobenzenesulfonylisourea n-butylamino' salt of p-nitrobenzenesulfonylisourea n-dodecylamino salt of 'p-aminobe'nzenesulfonylisourea diethanolamino salt of p aminobenzenesulfonylisourea ethanolaminosalt of p-'aminobenzenestilfonylisourea isourea n-butylamino salt of p-am1nobenzenesulfonylisourea n-butylamino salt of p-formylaminobenzenesulfonylisourea n-butylamino salt of p-acetylaminobenzenesulfonylisourea n-dodecylamino salt of p-formylaminobenzenesulfonylisourea n-dodecylamino salt of p-acetylaminobenzesulfonylisourea ethanolamino salt of p-formylaminobenzenesulfonylisourea ethanolamino salt of p-acetylaminobenzenesulfonylisourea diethanolamino salt of p-formylaminobenzenesulfonylisourea diethanolamino salt of p-acetylaminobenzenesulfonylisourea. di-isopropylarnino salt of p-nitrobenzenesulfonylisourea di-isopropylamino salt of p-aminobenzenesulfonylisourea di-isopro-pylamino salt of p-tformylaminohenzenesulfonylisourea di-isopropylamino salt of p-acetylaminobenzenesulfonylisourea dimethylamino salt of 1-(p-nitrobenzenesulfonyl)-3- propylisourea dimethylamino salt of l-(p-aminobenzenesulfonyl)-3- propylisourea dimethylamino salt of l-(p-formylaminobenzenesulfonyl)-3-propylisourea dimethylamino salt of l-(p-acetylaminobenzenesulfonyl)-3-propylisourea dimethylamino salt of 1-(p-nitrobenzenesulfonyl)-3- butylisourea dirnethylamino salt of 1-(p-aminobenzenesulfonyl)-3- butylisourea dimethylamino salt of l-(p-formylaminobenzenesulfonyl)-3-butylisourea dimethylamino salt of 1-(p-acetylaminobenzenesulfonyl)-3 butylisourea di-dodecylamino salt of l-(p-acetylaminobenzenesulfonyl)-3-ethylisourea tri-n-butylamino salt of l-(p-acetylaminobenzenesulfonyl)-3-methoxyisourea dipropargylamino salt of 1-(p-nitrobenzenesulfonyl)- 3-methyl-3-heptylisourea dioctylamino salt of 1-(3,4-dichlorobenzenesulfonyl)- 3-methyl-3-(3-hydroxyphenyl)isourea di-n-amylamino salt of 1-(p-chlorobenzenesulfonyl)- 3-butyne-2-isourea dipropylamino salt of 1-(p-cyanobenzenesulfonyl)-- 3,3-dimethylisourea di-n-amylamino salt of 1-(p-methoxybenzenesulfonyl)- 3-propoxyisourea triethylamino salt of 1-(2-chloro-5-nitrobenzenesulfonyl)-3-dodecylisourea di-n-butylamino salt of l-(3,5-dichloro-4-aminobenzenesulfonyl)-3-methylisourea diethylamino salt of 1-(p-nitrobenzenesulfonyl)-3-(3- tertiary butylcarbamoyloxyphenyl)isourea dimethylamino salt of 1-(p-aminobenzenesulfonyl-$- [4-(4-chlorophenoxy)phenyl]isourea diethylamino salt of l-(p-nitrobenzenesulfonyl)-3- propyne-Z-isourea dipropylamino salt of 1-(p-nitrobenzenesulfonyl)-3- (Z-methylcyclohexyl)isourea trimethylamino salt of 1-(p-nitrobenzenesulfonyl)-3- (1-cyclohexen-1-yl)-3-methylisourea ethanolamino salt of 1- (p-nitrobenzenesulfonyl)-3- (3-trifluoromethylphenyl isourea The following examples illustrate the invention. Parts and percent are by weight unless otherwise indicated.

The term plant system as used herein and in the appended claims means germinant seeds, emerging seedlings and established vegetation including the roots and above-ground portions.

EXAMPLE 2 The pre-emergent herbicidal activity of representative salts of substituted benzenesulfonyl ureas of this invention is demonstrated as follows:

A good grade of top soil is placed in aluminum pans and compacted to a depth of to A2" from the top of each pan. A predetermined number of seeds of each of several plant species are placed on top of the soil in the pans. The herbicidal compositions are applied t the soil by two methods:

(1) Application to the surface of the top soil layer and (2) Admixture with or incorporation in the top soil layer.

In the surface application method, the seeds are covered with a layer of prepared soil and the pans leveled. The herbicidal composition is applied by spraying the surface of the top layer of soil, prior to watering the seeds, with a solution containing a suflicient amount of active ingredient to obtain the desired rate per acre on the soil surface. In the soil incorporation method, the soil required to fill the pans is weighed and admixed with a herbicidal composition containing a known amount of active ingredient. The seeds are thencovered with the admixture and leveled. Initial watering is carried out by permitting the soil to absorb moisture through the apertured bottom of the pans.

The seed containing pans are placed on a wet sand bench and maintained for approximately 14 days under ordinary conditions of sunlight and watering. The plants are observed at the end of approximately 14 days and the results recorded. The herbicidal activity index is based on the average percent germination of each seed lot. The activity index is converted to a relative numerical scale for the sake of brevity and simplicity in the examples.

The pre-emergent herbicidal activity index used in the following example is defined as follows:

Numerical scale: Herbicidal activity 0 None. 1 Slight. 2 Moderate. 3 Severe.

The pre-emergent herbicidal activity of some of the salts of substituted benzenesulfonyl urea of this invention is recorded in Table I for a rate of five pounds per acre of the active ingredient in both surface and soilincorporation application. Compound (5) is by surface application, the remaining compounds are by soil incorporation.

TABLE I.-PRE-EMERGENT HERBICIDAL ACTIVITY Compound Plant species (1) (2) (3) (4) (5) (6) Morning glory Wild \ONH-OOHMMWNOHNNWNN cemvwrowoawwrrewoaww (1)=HeXamethyle11eirnine salt of p-nitrobeuzenesuliouylisoui'ea; (2)=Dial1y1amino salt of p-nitrobenzenesullonyllsourea.

(3) =Ethanolamino salt of p-nitrobenzenesulfonylisourea.

(4) =Diethanolamino salt of p-nitrobenzenesulfonylisourea.

(5) =Dodecylan1ino salt of p-niti'obenzenesulfonylisourea.

(6) =11-B utylamino salt of p-a1ninobenzenesullouylisourea.

EXAMPLE 3 this example is based on'the average percent injury of each plant species and is defined as follows:

Numerical scale: Herbicidal activity None.

1 Slight.

2 Moderate.

3 Severe.

4 Plants dead.

POST-EMER GENT HE RBIOIDAL ACTIVITY Compound Plant species (1) (2) (3) (4) (5) Morning glory 1 4 2 2 1 ild oat 0 4 1 1 4 Brome 1 4 1 '0 4 Rye grass 1 4 0 0 4 Radish 1 3 3 2 1 2 3 4 3 0 Rice 4 1 (1) -Dimethylamino salt of p-aoetylaminobenzenesulfonyllsourea. (2)Dimethylamino salt of p-aminobenzenesulfonylisourea. (3)-Diisopropylamino salt of p-ehlorobenzenesulfonylisourea.

(4) -Dimethylamino salt of 3 ,4 -dichlorobenzenesulfonylisourea. (5)-n-Butylamino salt of plormylaminobenzenesulfonylisourea. V

B Efl'ects of compound (2) were observed 5 weeks after spraying.

b Etiects of compound (5) were observed 4 weeks after spraying.

The amine salts of the benzenesulfonyl ureas have also shown herbicidal activity against perennial grasses such as Johnson grass, quack grass and Bermuda grass.

EXAMPLE 4 rate of equivalent to 200 gallons of solution per acre. This rate is equivalent to 5 lbs. per acre for the active'ingredient. The solution is applied to 6- to 8-inch tall quack and Bermuda grass and 12- to 15-inch tall Johnson grass. The sprayed plants were placed in a greenhouse and the effects were observed after 7 weeks.

The herbicidal activity index used in this example is based as follows:

Numerical scale: Hcrbicidal activity 0 No injury. 1 Slight injury. 2 Moderate injury. 3 Severe injury (top growth nearly or all dead). 4 Dead (both top and underground plant parts dead).

Bermuda Johnson Compound Quack grass grass grass (1)=Hexamothyleneimine salt of p-nitrobenzenesulionylisourea. (2)=Diallylamino salt of pmitrobenzenosultonylisourea. (3)=Etl1anolamino salt of p-nitrobenzenesulfonylisourea. (4)=Dietl1anolamino salt of p-nitrobenzenesulfonylisourca.

The herbicidal compositions of this invention comprise an active ingredient and one or more herbicidal adjuvants which can be solid or liquid extenders, carriers, diluents, conditioning agents and the like. Preferred herbicidal compositions containing the active ingredients of this invention have been developed so that the active ingredients can be used to the greatest advantage to modify the growth of plant systems in soil. The preferred compositions comprise certain Wettable powders, aqueous suspensions, dust formulations, granules, emulsifiable oils and solutions in solvents. in general these preferred compositions can all contain one or more surface-active agents.

Surface-active agents which can be used in the herbi- V cidal compositions of this invention are set out, for example in Searle U.S. Pat. 2,426,417, Todd US Pat.

2,655,447, Jones US. Pat. 2,412,510 and Lenher US. Pat. 2,139,276. A detailed list of such agents is also set forth by J. W. McCutcheon in Soap and Chemical Specialties, November 1947, page 8011 et seq., entitled Syn- 'thetic Detergents, Detergents and EmulsifiersUp to Date (1960), by J. W. McCutcheon, Inc., and Bulletin- E-607 of the Bureau of Entomology and Plant'Quarantine of the USDA. In general less than 15 parts by weight of the surface active agent is present per 100 parts by'weight of the herbicidal composition.

Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents.

or acid amides, long chain acid esters of sodium iso-' thionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum-sulfonates, sulfonated vegetable o1ls.and ditertiary acetylinic 'glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin ,sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate,"polymethylene bi'snaphthalenesulfonate and sodium N-rnethyl-N-(long chain acid) taurates. 1 p .1

The, Wettable powders compositions. of :this invention usually, contain from .about to about5 to about partsof active ingredient, from'about 0.25 to about:3.0. parts. of wetting agent, from about 0.25 to, about 7: parts of dispersant and from about -4.5 to about-94.5 parts .of inert solid extender, all parts being by weight 9 of the total composition. Where required from about 0.1 to 2.0 parts by Weight of the solid inert extender can be replaced by a corrosioin inhibitor or anti-foaming agent or both.

Aqueous suspensions are usually prepared by mixing together an aqueous slurry of water-insoluble active ingredient in the presence of dispersing agents to obtain a concentrated slurry of very finely-divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed coverage is very uniform.

Dusts are dense finely-divided particulate compositions which are intended for application to the soil in dry form. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily wind-borne to areas where they are of no value. Dusts contain primarily an active ingredient and a dense, freeflowing, finely-divided particulate extender. However, their performance is sometimes aided by the inclusion of a Wetting agent such as those listed hereinbefore under wettable powder compositions and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. Suitable classes of grinding aids are natural clays, diatomaceous earth and synthetic minerals derived from silica or silicate. Preferred grinding aids include attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates.

The inert finely-divided solid extender for the dusts can be of vegetable or mineral origin. The solid extenders are characterized by possessing relatively low surface areas and are poor in liquid absorption. Suitable inert solid extenders for herbicidal dusts include micaceous talcs, pyrophyllite, dense kaolin clays, ground calcium phosphate rock and tobacco dust. The dusts usually contain from about 0.5 to 99 parts active ingredient, to 50 parts grinding aid, 0 to 3 parts wetting agent and 1 to 99.5 parts dense solid extender, all parts being by weight based on the total weight of the dust.

The wettable powders described above may also be used in the preparation of dusts. While such wettable powders could be used directly in dust form, it is more advantageous to dilute them by blending with the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and anti-foam agents may also be found as components of a dust.

Emulsifiable oils are usually solutions of active ingredient in water-immiscible solvents together with a surfactant. Suitable solvents for the active ingredient of this invention include hydrocarbons and water-immiscible ethers, esters or ketones. Suitable surfactants are anionic, cationic and non-ionic such as alkyl aryl polyethoxy alcohols, alkyl and alkyl aryl polyether alcohols, polyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty esters, fatty alkyllol amide condensates, amine salts of fatty alcohol sulfates together with long chain alcohols and oil soluble petroleum sulfonates or mixtures thereof. The emusifiable oil compositions generally contain from about 5 to 95 parts active ingredient, about 1 to parts surfactant and about 4 to 94 parts solvent, all parts being by Weight based on the total weight of emulsifiable oil.

Granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender. In order to aid leaching of the active ingredient from the particulate, a surfactant such as those listed herein-before under wettable powders can be present in the composition. Natural clays, pyrophyllites and vermiculite are examples of operable classes of particulate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate attapulgite or heat expended, particulate vermiculite, and the finely-divided clays such as kaolin clays, hydrated attapulgite or ben- 1O tonitic clays. These extenders are sprayed or blended with the active ingredient to form the herbicidal granules.

The mineral particles which are used in the granular herbicidal compositions of this invention usually have a size range of 10 to 100 mesh, but preferably such that a large majority of the particles have from 14 to 60 mesh with the optimum size being from 20 to 40 mesh. Clay having substantially all particles between 14 and mesh and at least about 80 percent between 20 and 40 mesh is particularly preferred for use in the present granular compositions. The term mesh as used herein means U.S. Sieve Series.

The granular herbicidal compositions of this invention generally contain from about 1 part to about 30 parts by weight of a salt of a substituted benzenesulfonyl urea per parts by weight of clay and 0 to about 5 parts by weight of wetting agent per 100 parts by weight of clay. The preferred herbicidal granular compositions contain from about 5 parts to about 25 parts by weight of active ingredient per 100 parts by weight of clay.

The herbicidal compositions of this invention can also contain other additaments, for example, fertilizers, other heribicides, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants.

The compounds of this invention may be used in combination with known herbicides in order to provide enhanced biological effectiveness. The use of various herbicides in combination at the time of a single application or sequentially is common in practice. Herbicde's which may be used in combination with the compounds of this invention include but are not limited to: substituted phenoxyaliphatic acids such as 2,4-dichlorophenoxyacetic acid;

2,4,S-trichlorophenoxyacetic acid,

2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof;

triazine derivatives, such as 2-chloro-4-ethylamino-6- isopropylamino-'s-triazine;

2,4-bis(isopropylamino)-6-methoxy-s-triazine and Z-methylmercapto-4,6-bis(isopropylamino)-s-triazine;

urea derivatives such as 3-(3,4-dichlorophenyl)-l,1-dimethylurea and 3-(m-trifluoromethylphenyl)-1;,1-dimethylurea and 3-(3,4-dich1orophenyl)-1-methoxy-1- methylurea;

pyridylium derivatives such as 1:1'-ethylene-2,2-dipyridylium dihalide;

acetanilides such as N-isopropyl-alpha-chloroacetanilide,

i rd 2- chloro-2',6'-diethylN-methoxymethyl acetani- 1 e; acetamides such as N,N-diallyl-alphachloroacetamide, carbamates such as ethyl-N,N-di-n-propylthiolcarbamate,

and 2,3-dichloroallyl diisopropylthiolcarbamate; substitulted uracils such as 5-bromo-3-sec-butyl,-6-methyluraci substituted anilines such as N,N-dipropyl-alpha,alpha,

alpha-trifluoro-Z,6-dinitro-p-toluidine; pyridazone derivatives such as 5-amino-4-chloro-2- phenyl-3- 2H) -pyridazinone, and the like.

Fertilizers useful in combination with the active ingredients include, for example ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

When operating in accordance with the present invention, effective amounts of the salts of substituted benzenesulfonyl ureas are dispersed on or in the soil or plant growth media and applied to plant systems in any convenient fashion. Application to the soil or growth media can be carried out by simply mixing with the media, by applying to the surface of the soil and thereafter dragging or discing into the soil to the desired depth, or by employing a liquid carrier to accomplish the penetration and impregnation. The application of liquid and particulate solid herbicidal compositions to the surface of soil or to plant systems can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. In a further method, the distribution of the active ingredients in soil can be carried out by admixture with the water employed to irrigate the soil. In such procedures, the amount of water can be varied with the porosity and water holding capacity of the soil to obtain the desired depth of distribution of the herbicide.

The application of an effective or herbicidal amount of the salts of substituted benzene'sulfonyl ureas to the soil or growth media or plant systems is essential and critical for the practice of one embodiment of the present invention. The exact amount of active ingredient to be employed is dependent upon the response desired in the plant as well as such other factors as the plant species and stage of development thereof, the specific soil and depth at which the active ingredients are distributed in the soil and the amount of rainfall as Well as the specific salt of the substituted benzenesulfonyl urea employed. In foliar treatment for the control or modification of vegetative growth, the active ingredients are applied in amounts from about 1 to about 50 or more pounds per acre. In applications to soil for the control or modification of the growth of germinant seeds emerging seedlings and established vegetation, the active ingredients are applied in amounts from about 1 to about 50 or more pounds per acre. It is believed that one skilled in the art can readily determine from this specification, including examples, the application rate for any specific situation.

The terms soil and growth media are employed in the present specification and claims in their broadest sense to be inclusive of all conventional soils as defined in Websters New International Dictionary, Second Edition, Unabridged (1961). Thus, the terms refer to any substance or media in which vegetation may take root and grow, and are intended to include not only earth but compost, manure, muck, humus, sand and the like, adapted to support plant growth.

While the illustrative embodiments of the invention have been described herein before with particularity, it Will be understood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and description set forth herein but rather the claims be construed as encompassing all the features of patentable novelty which reside in the present invention including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

What is claimed is:

1. A method of controlling the growth of plants which comprises exposing the plant system to a herbicidally effective amount of one or more compounds of the formula wherein R is selected from the group consisting of chlorine, bromine, alkyl having a maximum of four carbon atoms, nitro, amino, and the group that when n is one R is substituted in the 4'-position; R and R are each independently selected from the group 12 consisting of hydrogen and alkyl having a maximum of twelve carbon atoms; A is selected from the group consisting of (a) Hm l I--N (0112)...

and

IINR7 wherein R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of twelve carbon atoms, alkenyl having a maximum of six carbon atoms, and monohydroxyalkyl having a maximum of six carbon atoms, In is an integer from four to seven, and R is selected from the group consisting of alkyl having a maximum of twelve carbon atoms, alkenyl having a maximum of six carbon atoms, and monohydroxyalkyl having a maximum of six carbon atoms.

2. A method of claim 1 in which the compound is of the formula 3. A method of claim 2 in which R and R are hydrogen and R is monohydroxyalkyl.

4. A method of claim 3 in which R is 2-hydroxyethyl.

5. A method of claim 4 in which the compound is the ethanolamine salt of p-nitrobenzenesulfonylisourea.

6. A method of claim 2 in which R is hydrogen and R and R are monohydroxyalkyl.

7. A method of claim 6 in which R and R are Z-hydroxyethyl.

8. A method of claim 7 in which the compound is the diethanolamine salt of p-nitrobenzenesulfonylisourea.

9. A method of controlling perennial grasses which comprises applying to the grasses a herbicidally effective amount of one or more of the compounds of the formula wherein R is selected from the group consisting of chlorine, bromine, alkyl having a maximum of four carbon atoms, nitro, amino, and the group wherein R is hydrogen or alkyl having a maximum of four carbon atoms; 11 is the integer one to three, provided that when n is one R is substituted in the 4-position; R and R are each independently selected from the group consisting of hydrogen and alkyl having a maximum of twelve carbon atoms; R and R are each independently selected from the group consisting of hydrogen, alkyl having a maximum of twelve carbon atoms, alkenyl having a maximum of six carbon atoms, and monohydroxyalkyl having a maximum of six carbon atoms; and R is selected from the group consisting of alkyl having a maximum of twelve carbon atoms, alkenyl having a maximum of six carbon atoms, and monohydroxyalkyl having a maximum of six carbon atoms.

10. A method of claim 9 in which R and R' are hydrogen and R is monohydroxyalkyl.

11. A method of claim 10 in which R is 2-hydroxyethyl.

12. A method of claim 11 in which the compound is the ethanolamine salt of p-nitrobenzenesulfonylisourea.

13. A method of claim 9 in which R is hydrogen and R and R are monohydroxyalkyl.

14. A method of claim 13 in which R and R are 2-hydroxyethyl.

15. A method of claim 14 in which the compound is the diethanolamine salt of p-nitrobenzenesulfonylisourea.

16. The process of selectively controlling the growth of undesirable grass in an area in which desirable grasses are presi nt, comprising the step of applying to said area a herbicidally effective amount of a compound having the formula.

References Cited UNITED STATES PATENTS 3/1943 Haack 260397.7 8/1944 Roflin, Jr. et a1. 260-3977 JAMES O. THOMAS, JR, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,736,122 D d May 29, 197} Inventor(s) Ching C- Tung et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, in the section above the Abstract of the Disclosure, immediately following "65132" please insert assignor to Monsanto Company, St. Louis, Mo.

Column 5, line 44 reading "wherein R and -R are each selected from the group" please insert as follows wherein R and R are each independently selected from the group Column 4, the second line of the second formula should read (3 R RQSOZNHC-N-R2 Column 7, at the end of line 26 reading "The active ingredient" should read The active ingredients Signed and sealed this 12th day of February 1974.

(SEAL) Attest:

EDWARD M.PLETCHER,'JR. I C. MARSHALL DANN Attestlng Officer Commissioner of Patents FORM PC1-1050 (10- USCOMM-DC sows-ps9 US. GOVERNMENT PRINTING OFFICE: I969 0-366-212 

